Low volatile organic additives for paints and use thereof

Abstract

The present technology relates generally to compositions comprising an aqueous dispersion of a polymeric binder resin, a pigment, and an additive. In particular, the additive comprises a compound of Formula (I).

Description

LOW VOLATILE ORGANIC ADDITIVES FOR PAINTS ANDUSE THEREOFCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Appl. No. 63 / 566,833, filed March 18, 2024, the contents of which are incorporated herein by reference in their entirety for any and all purposes.TECHNICAL FIELD

[0002] The present technology relates to paints or water-based coating formulations with low (or zero) volatile organic compounds (VOC) and use thereof. The present invention also provides methods of reducing the VOC content and / or methods of reducing toxicity of a composition (e.g., paints or water-based coating formulations).BACKGROUND

[0003] Water-based industrial coating compositions typically use water reducible or water dispersible polymers as binders in the aqueous composition. These polymers contain acid functional groups that require at least partial neutralization in order for the polymers to be solubilized or dispersed and subsequently function as binders. Amino alcohol additives are often used in water-based coating formulations to stabilize pH and provide a high-quality dry film.

[0004] Coating products with low (or zero) volatile organic compound content are desirable for environmentally sustainable applications. In many geographies, paint manufacturers are facing regulations to reduce the volatile organic content of their formulations. Additives must have a sufficiently high boiling point to be considered low (or zero) VOC (e.g., above 250 °C or above 280 °C). Emission testing and gas chromatography testing may also be required depending on the geographic region.

[0005] In addition, neutralization efficiency is important because a high dose of amino alcohol can negatively impact the quality of the dry film. Existing technology that uses N- butyldiethanolamine requires a high dose of amino alcohol to achieve a stable pH, or inorganic neutralizers leading to detrimental macroscopic performances of the final dry film.

[0006] Thus, as explained above and in more details below, there remains a need for compositions (e.g., paints or water-based coating formulations) comprising low (or zero) VOC content, particularly compositions with a reduced dose of VOC (or zero) content and reduced toxicity.SUMMARY

[0007] The present technology provides compositions comprising an aqueous dispersion of a polymeric binder resin, and an additive (e.g., a low or zero VOC additive). The compositions may further comprise a pigment. The present invention also provides methods of reducing the VOC content and / or methods of reducing toxicity of a composition (e.g., paints or water-based coating formulations).

[0008] In one aspect, provided herein is a composition comprising an aqueous dispersion of a polymeric binder resin, optionally a pigment, and an additive, wherein the additive comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided thatthe compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or10 carbon atoms.

[0009] In a further aspect, the present technology provides a coating comprising the dried composition described herein.

[0010] In another aspect, provided herein is a method for reducing the volatile organic compound content of a composition comprising an aqueous dispersion of a polymeric binder resin and optionally a pigment, the method comprising using an effective amount of a neutralizing agent in the composition wherein the neutralizing agent comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.

[0011] In another aspect, provided herein is a method for reducing toxicity of a coating composition comprising an aqueous dispersion of a polymeric binder resin and optionally a pigment, the method comprising using as a neutralizing agent in the paint or coating an effective amount of a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.

[0012] In a further aspect, provided herein is a method comprising adding to a composition comprising an aqueous dispersion comprising a pigment and / or polymer binder resin an effective amount of an additive to raise the pH of the composition, stabilize the composition, and / or at least partially neutralize any acidic compounds in the composition, wherein the additive comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.

[0013] In any embodiments described herein, the pigment is present in the composition.BRIEF DESCRIPTION OF THE DRAWINGS

[0014] FIG. 1 provides the titration curve of different additives 2-amino-2-methyl-l- propanol (AMP), 2-amino-2-ethylpropane- 1,3 -diol (AEPD), NaOH, 2,2'- (butylazanediyl)bis(ethan-l-ol) (NBDEA), Compound 1, and Compound 13, respectively) with HC1.

[0015] FIG. 2 provides the dispersant demand curve of TiO2 in the presence of the corresponding additives and without any other dispersing agents.

[0016] FIGS. 3A-3B provide the dispersant demand curve of TiO2 by % wt of additives and without any other dispersing agents. FIG. 3A provides the dispersant demand curve of TiCh with AMP, NBDEA, Compound 1, AEPD, and Compound 13, respectively. FIG. 3B provides the dispersant demand curve of TiCh with AMP, DEA, and Compound 1, respectively.

[0017] FIG. 4A provides the dispersant demand curve of TiCh with 0.05 wt% of the corresponding additives (NBDEA, Compound 1, and Compound 13, respectively) and in the presence of Orotan 731. FIG. 4B provides the dispersant demand curve of TiCh with 0.15 wt% of the corresponding additives (NBDEA, Compound 1, and Compound 13, respectively) and in the presence of Orotan 731.

[0018] FIGS. 5A-5D provides graphs showing the evolution of the pH for all additives tested (AEPD, AMP, Compound 1, NaOH, and NBDEA, respectively) at time zero and at 84 days. FIG. 5A is a box plot that compares pH at t=0 (left-hand box) and t=84 days (righthand box) for each additive. FIG. 5B is a box plot that shows the pH slope for each additive. FIG. 5C is a box plot that shows the magnitude of the change in pH over time (pH tO - pH t84) for each additive. FIG. 5D shows the change over time in pH for each additive.

[0019] FIGS. 6A-6B provide box plot representations of the gap between the initial pHo and pHs4 (about 3 months) at two different levels of additive for Compound 13 (FIG. 6A) and Compound 1 (FIG. 6B).

[0020] FIG. 7 provides initial gloss distributions for all angles and all additives (AEPD, AMP, Compound 1, NaOH, and NBDEA, respectively) via box plot representations.

[0021] FIG. 8 provides correlation of the gloss 60° and the concentration of additives (AEPD, AMP, Compound 1, NaOH, and NBDEA, respectively).

[0022] FIG. 9 provides standard deviation of the gloss 60° analysis for each additive (AEPD, AMP, Compound 1, NaOH, and NBDEA, respectively).

[0023] FIG. 10 provides comparison of the initial values of L*, a*, and b* for each additive (AEPD, AMP, Compound 1, NaOH, and NBDEA, respectively).

[0024] FIG. 11 provides comparison of the initial values of a*, and b* for each additive (AEPD, AMP, Compound 1, NaOH, and NBDEA, respectively) separated with both additive concentrations.

[0025] FIG. 12 provides standard deviation of both L* and b* for each additive (AEPD, AMP, Compound 1, NaOH, and NBDEA, respectively).

[0026] FIG. 13 provides box plot representation of each contrast ratio distributions, and the standard deviation for each additive (AEPD, AMP, Compound 1, NaOH, and NBDEA, respectively).

[0027] FIG. 14 provides box plot representation of the difference between initial and final contrast ratios for each additive tested after 3 months (AEPD, AMP, Compound 1, NaOH, and NBDEA, respectively).

[0028] FIG. 15 provides distribution of the hardness results for each additive (AEPD,AMP, Compound 1, NaOH, and NBDEA, respectively).

[0029] FIG. 16 provides L evolution (in function of time) of each additive upon storage at 50 °C.DETAILED DESCRIPTION

[0030] The following terms are used throughout as defined below.

[0031] As used herein and in the appended claims, singular articles such as “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0032] As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term - for example, “about 10 wt%” would be understood to mean “9 wt% to 11 wt%.” It is to be understood that when “about” precedes a term, the term is to be construed as disclosing “about” the term as well as the term without modification by “about” - for example, “about 10 wt%” discloses “9 wt% to 11 wt%” as well as disclosing “10 wt% ”

[0033] The phrase “and / or” as used in the present disclosure will be understood to mean any one of the recited members individually or a combination of any two or more thereof - for example, “A, B, and / or C” would mean “A or B or C; A and B; A and C; B and C; or the combination of A, B, and C.”

[0034] The term "alkyl" refers to a group, whether alone or as part of another group (e.g., in dialkylamino), encompasses straight and branched chain aliphatic groups (z.e., saturated hydrocarbyl chains), and, unless otherwise indicated, has 1-10, alternatively 1-8, or alternatively 1-6 alkyl carbon atoms. Preferred alkyl groups include, without limitation,methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl. Unless otherwise indicated, the alkyl group is optionally substituted with 1, 2, or 3, preferably 1 or 2, more preferably 1, substituents that are compatible with the compounds, monomers, and polymers described herein. In some embodiments, the alkyl group is unsubstituted.

[0035] The term "alkoxy" refers to a group in which an oxygen attached to a saturated straight or branched chain alkyl group. Unless otherwise indicated, the alkoxy group contains 1 to 6 carbon atoms (e.g. methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentyloxy, iso-pentyloxy, n-hexyloxy or isohexyloxy), and preferably 1 to 4 carbon atoms. Representative examples of preferred alkoxy groups include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy. In some embodiments, the alkoxy group is unsubstituted.

[0036] The term "cycloalkyl" refers to saturated cyclic hydrocarbon groups. Unless otherwise indicated, the cycloalkyl group has 3 to 12 ring carbon atoms, alternatively 3 to 8 ring carbon atoms, or alternatively 3 to 6 ring carbon atoms. Preferred cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, and cyclohexyl. Unless otherwise indicated, the cycloalkyl group is optionally substituted with 1, 2, or 3, preferably 1 or 2, more preferably 1 alkyl group. In some embodiments, the alkyl group may include 1-6 carbon atoms, preferably the alkyl group is unsubstituted and includes 1-4 carbon atoms. In some embodiments, the cycloalkyl group is unsubstituted.

[0037] The term “heterocycloalkyl” as used herein refers to non-aromatic ring compounds containing 5 or more ring members, of which at least three are carbon atoms and at least one is a nitrogen atom. In some embodiments, the heterocyclyl group contains 1 or 2 heteroatoms. In some embodiments, the heterocyclyl group may include at least 4 or at least 5 carbon atoms. Typically, the heterocycloalkyl group is unsubstituted.

[0038] Groups described herein having two or more points of attachment (z.e., divalent, trivalent, or polyvalent) within the compound of the present technology are designated by use of the suffix, “ene.” For example, divalent alkyl groups are alkylene groups, divalent cycloalkyl groups are cycloalkylene groups, and so forth. Substituted groups having a singlepoint of attachment to the compound of the present technology are not referred to using the “ene” designation. Thus, e.g., chloroethyl is not referred to herein as chloroethylene.

[0039] In general, “substituted” refers to an alkyl group, as defined above in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms. Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom. In some embodiments, a substituted group is substituted with 1, 2, or 3 substituents. Examples of substituent groups include, but are not limited to, hydroxyl, amino, thiol, nitro, halo, ester, amido, carbonyl, or carboxylic acid. Unless otherwise indicated, the foregoing substituent groups are not themselves further substituted.

[0040] Unless stated otherwise, all the molecular weight (z.e., molar mass) data, numberaverage molecular weight data Mn or weight-average molecular weight data Mw stated in the present description are molar masses, which can be determined by gel permeation chromatography (GPC).

[0041] As used herein, “binder” refers to the film forming component of a coating. To form the films, the polymeric binder (z.e., polymer) may be coalesced. Coalescence refers to the process where first the solvent (e.g., water) evaporates causing the polymeric binders to be drawn together and then fused into irreversibly bound networked structures, so that the coating cannot redissolve in the original carrier solvent. Polymeric binder resin is also referred to as “binder” and “polymeric binder.”

[0042] As used herein, “water-reducible polymeric binder” (z.e., water-reducible binder) refers to a hydrophobic resin that has been modified to contain acidic groups such that the binder is soluble in water with at least partial neutralization. As used herein, “water- dispersible polymeric binder” (z.e., water-dispersible binder) refers to resins with acidic groups that could be dispersed in a continuous aqueous medium with at least partial neutralization.

[0043] As used herein, “substantially free” refers to less than about 2 wt% of the specified component based on the total weight of the composition. In some embodiments, thecomposition may include less than about 1 wt%, less than about 0.5 wt%, or less than about 0.1 wt% of the specified component. In some embodiments, the composition may free of detectable amounts of the component.Compositions comprising low or zero VOC additives

[0044] Provided herein are compositions (e.g., a paint or a coating) with low or zero VOC content. In some embodiments, the composition may be an aqueous based coating e.g., paint). In some embodiments, the composition may be an aqueous dispersion or emulsion. Typically, the compositions described herein include an aqueous dispersion of a polymeric binder resin, a pigment, and an additive (e.g., a low or zero VOC additive). In some embodiments, the additive may include or may be a neutralizing agent such as a low or zero VOC neutralizing agent.

[0045] As used herein, term “low VOC” (i.e., low volatile organic compound) or “zero VOC” (i.e., zero volatile organic compound) refers to carbon compounds having a boiling point above 250 °C at normal atmospheric pressure (i.e., 101,325 Pa). In some embodiments, “low VOC” or “zero VOC” refers to carbon compounds having a boiling point above 280 °C.

[0046] In one aspect, the present technology provides compositions (e.g., a paint or a coating) comprising an aqueous dispersion of a polymeric binder resin, a pigment, and an additive, wherein the additive comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH.

[0047] In some embodiments, the compound of Formula (I) described herein has 1 or 2 hydroxy groups. In some embodiments, the compound of Formula (I) described herein has 6, 7, 8, 9, or 10 carbon atoms.

[0048] In some embodiments (e.g., a compound of Formula (I)), R1may be Ci-4 alkyl optionally substituted with OH. For example, R1may be (CH2)3CH3, CH3, CH2CH(OH)CH3, or CH2CH2OH. In some embodiments R1is CH2CH2OH.

[0049] In some embodiments, the compound of Formula (I) has a structure of Formula(II)

[0050] In some embodiments (e.g., a compound of Formula (I) or Formula (II)), R1’ is Ci- 4 alkyl optionally substituted with OH (e.g., CH2CH2OH). For example, R1’ may be (CH2)3CH3, CH3, CH2CH(OH)CH3, or CH2CH2OH. In some embodiments R1’ is CH3 or CH2CH2OH.

[0051] In some embodiments (e.g., a compound of Formula (I) or Formula (II)), R4and R4are both H. In some embodiments (e.g., a compound of Formula (I) or Formula (II)), R4and R4are both Ci-4 alkyl optionally substituted with OH. In some embodiments, R4and R4are both OH substituted Ci-4 alkyl (e.g., CH2CH2OH) or both unsubstituted Ci-4 alkyl. In some embodiments, one of R4and R4is unsubstituted Ci-4 alkyl (e.g., CH3), and the other is OH substituted Ci-4 alkyl (e.g., CH2CH2OH).

[0052] In some embodiments (e.g., a compound of Formula (I) or Formula (II)), R2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH. For example, R2, R2, R3, and R3may be each independently selected from H, CH3, CH2CH3, or CH2OH.Exemplary compounds of Formula (I)

[0053] In some embodiments, the additive may comprise or may be a compound of Formula (I). In some embodiments, the additive may comprise or may be any one described in Table A, or a combination thereof.Table A. Exemplary compounds of Formula (I).

[0054] In some embodiments, the additive may comprise or may be Compound 1 (2,2'- ((2-amino-2-methylpropyl)azanediyl)bis(ethan-l-ol)). In some embodiments, the additive may comprise or may be Compound 13 (2,2'-(ethane-l,2-diylbis(methylazanediyl))bis(ethan- l-ol)). In some embodiments, the additive may comprise or may be a combination of Compound 1 and Compound 13.

[0055] The additives described herein (e.g., a compound of Formula (I) such as Compound 1 or Compound 13) have a sufficiently high boiling points to each be considered low VOC. For example, the compound of Formula (I) has a boiling point above 250 °C at one atm. In some embodiments of compounds of Formula I, including Compound 1 and Compound 13, the boiling point is above 280°C at 1 atm (determined by distillation).

[0056] Compositions of the present technology may include a wide range of amounts of the additive described herein (e.g., a compound of Formula (I)). For example, the compositions may include from about 0.01 wt% to about 10 wt% of the additive (e.g., a compound of Formula (I)) based on the total weight of the composition, including from about 0.05 wt% to about 5 wt%, from about 0.05 wt% to about 2 wt%, or from 0.05 wt% to about 0.5 wt%. In some embodiments, the compositions may include about 0.01 wt%, about 0.05 wt%, about 0.1 wt%, about 0.15 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.75 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt%, of the additive, or a range between and including any two of the foregoing values. In some embodiments, the compositions may include from about 0.05 wt% to about 0.5 wt% of the additive based on the total weight of the composition.

[0057] In some embodiments, the composition may further include one or more neutralizing agents (e.g. hydroxides, amines, and carbonates) other than the present additives (i.e., the compounds of Formulas (I)). In some embodiments, the compositions furtherinclude one or more additional neutralizing agents that are low or zero VOC neutralizing agents other than the compounds of Formula (I). In some embodiments, an inorganic base may be included in the composition as the additional neutralizing agent.

[0058] In some embodiments, the composition may be substantially free of additives (or neutralizing agents) that are not low (or zero) VOC. For example, the composition may be substantially free of a neutralizing agent having a boiling point of less than 250 °C. In some embodiments, the composition does not contain a neutralizing agent having a boiling point of less than 250 °C. In some embodiments, the composition may be substantially free or free of ammonia (NH3). In some embodiments, the composition may be substantially free of one or more selected from 2-amino-2-methyl-l -propanol (AMP), 2-amino-2-ethylpropane- 1,3 -diol (AEPD), 2,2'-(butylazanediyl)bis(ethan-l-ol) (NBDEA), 2,2'-(Ethane-l,2- diylbis(methylazanediyl))diethanol, and 2-{ [2-(dimethylamino)ethyl]methylamino}ethanol. In some embodiments, the composition does not contain one or more selected from 2-amino- 2-methyl-l -propanol (AMP), 2-amino-2-ethylpropane-l,3-diol (AEPD), 2,2'- (butylazanediyl)bis(ethan-l-ol) (NBDEA), 2,2'-(Ethane-l,2- diylbis(methylazanediyl))diethanol, 2-{[2-(dimethylamino)ethyl]methylamino}ethanol.

[0059] Neutralizing agents are often included in formulations to raise the pH to a desired value, e.g., to 7, 8, 9, 10, 11, 12, 13, or a range between and including any two of the foregoing values. In some embodiments, the compositions may have a pH of 7, 8, 9, 10, 11, 12, 13, or a range between and including any two of the foregoing values. In some embodiments, the compositions may have a pH range of about 7 to about 13 or about 7 to about 10.

[0060] Compositions of the present technology include water. The water may be used as a solvent and / or as a thinner when preparing and / or applying the coating composition. In some embodiments, the compositions may include at least about 20 wt% water, at least about 25 wt% water, at least about 30 wt% water, at least about 35 wt% water, at least about 40 wt% water, at least about 45 wt% water, at least about 50 wt% water, at least about 55 wt% water, at least about 60 wt% water, or a range between and including any two of the foregoing values. In some embodiments, the compositions may include about 20 wt% toabout 99 wt% water, about 35 wt% to about 97 wt%, about 45 wt% to about 95 wt%, about 50 wt% to about 93 wt%, or a range between and including any two of the foregoing values. In some embodiments, the compositions may include about 20 wt% to about 80 wt% water.Binders

[0061] In some embodiments, a composition as described herein (e.g., a paint or a coating) comprises a binder (e.g., a polymeric binder resin). At times, the polymeric binder resin may be a water-reducible polymeric binder, a water-dispersible polymer, or an emulsion polymer. Binders include polymers such as a polyacrylate, polyvinyl versatate, polyethylenevinyl acetate, polyester (e.g., polyester polyols and polyester polymers with one or more olefins), or a combination of two or more thereof. The polyacrylate may be a homopolymer or a copolymer. Exemplary copolymers of polyacrylate include polyvinyl acrylate, polyvinyl ver satate-acry late, polystyrenyl acrylate, or a combination of two or more thereof. In some embodiments, the binder may be a latex binder. In some embodiments, the binder may be an alkyd binder. The binders provided herein may be used individually in the compositions or may be used in combination as a simple blend or as a hybrid type copolymer.

[0062] The amount of the binder resins in the formulations of the present technology can be the amount conventionally used in paint and coating formulations, which can vary widely due to the desired gloss / sheen range, and also the solids concentration, of a specific paint formulation. For example, the compositions of the present technology may include from about 10 wt% to about 80 wt% polymeric binder resin based on the total weight of the composition, including from about 15 wt% to about 65 wt%, or from about 40 wt% to about 60 wt%. In some embodiments, the compositions may include about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, or about 80 wt%, of the polymeric binder resin, or a range between and including any two of the foregoing values. In some embodiments, the composition includes from about 20 wt% to about 60 wt% polymeric binder resin based on the total weight of the composition.

[0063] In some embodiments, the polymeric binders used herein include acid functional groups such as carboxyl, sulfonyl, phosphonyl, and / or phosphoric acid groups. In someembodiments, the acid functional groups are carboxyl groups. In some embodiments, the polymeric binders may have acid values of about 2 to about 200 mg KOH / g. In some embodiments, the polymeric binders may have acid values of about 5 to about 150 mg KOH / g or about 10 to about 100 mg KOH / g.

[0064] In some embodiments, the additive (e.g., one or more selected from a compound of Formula (I) and additional neutralizing neutralizes) neutralizes at least about 20% of the acid functional groups on the polymeric binder (e.g., at least about 30%, at least about 40%, or at least about 50%). In some embodiments, the additive neutralizes about 20% to about 100% of the acid functional groups on the polymeric binder (e.g., about 30% to about 90% or about 40% to about 80%. In some embodiments, the molar ratio of the additive to the acid functional groups on the polymeric binder may be about 1 :5 to about 5: 1 (e.g., about 1 :4 to about 2:1, about 1 :3 to about 2: 1, or about 1 :2 to about 1 : 1).

[0065] The binders of the present technology may be prepared by way of a wide range of processes. For example, the binders may be prepared in organic phase or in melt and then converted into water, the binder resin could also be prepared by emulsion polymerizations, or any other method known to those of skill in the art.Pigments

[0066] In some embodiments, a composition as described herein (e.g., a paint or a coating) comprises a pigment. Pigments may be included to provide hiding power and the desired color to the final coated material and may also be used to provide bulk to the paint or coating. All color and / or special effect-giving pigments of organic or inorganic type used in paints and coatings are suitable for use. In some embodiments, a composition as described herein comprises a pigment selected from the group consisting of titanium dioxide (TiCh), calcium carbonate, silica (SiCh), kaolin, and barium sulfate. In some embodiments, a composition as described herein comprises titanium dioxide and a colorant.

[0067] “Colorants,” as used herein, include dyes, pigments, and pre-dispersions, among others. Colorants are pigments that provide color. Colorants include red, white, blue, black, and yellow. As used herein, “pigment” refers to finely ground, insoluble material suspendedin a medium, which changes the color of reflected or transmitted light through wavelength- selective absorption. Pigments typically possess high tinting strength properties and are stable in solid form at ambient temperatures. Pigments can be natural or synthetic products. While multiple pigments may be present in end-use paints or coatings, it is also possible to use only white pigment, such as titanium oxide, perhaps in combination with extender pigments. Any other desired pigments of various colors (including more white pigment) can optionally be included in the compositions. Examples include colors such as yellow, magenta, and cyan. As a black coloring agent, carbon black, and a coloring agent toned to black using the yellow / magenta / cyan coloring agents. Colorants may be used singly, in a mixture, or as a solid solution. In various embodiments, pigments may be provided in the form of raw pigments, treated pigments, pre-milled pigments, pigment powders, pigment presscakes, pigment masterbatches, recycled pigment, and solid or liquid pigment predispersions. As used herein, a raw pigment is a pigment particle that has had no wet treatments applied to its surface, such as to deposit various coatings on the surface. Raw pigment and treated pigment are further discussed in PCT Publication No. WO 2005 / 095277 and U.S. Patent Application Publication No. 20060078485, the relevant portions of which are incorporated herein by reference. In contrast, a treated pigment may have undergone wet treatment, such as to provide metal oxide coatings on the particle surfaces. Examples of metal oxide coatings include alumina, silica, and zirconia. Recycled pigment may also be used as the starting pigment particles, where recycled pigment is pigment after wet treatment of insufficient quality to be sold as coated pigment. Exemplary colorant particles include, but are not limited to, pigments such as yellow coloring agent, compounds typified by a condensed azo compound, an isoindolynone compound, an anthraquinone compound, an azometal complex methine compound, and an allylamide compound as pigments may be used. As a magenta coloring agent, a condensed azo compound, a diketopyrrolopyrrole compound, anthraquinone, a quinacridone compound, a base dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound, and a perylene compound may be used. As a cyan coloring agent, a copper phthalocyanine compound and its derivative, an anthraquinone compound, a base dye lake compound, and the like may be used.

[0068] Additional examples of pigments can include, but are not limited to, titanium dioxide, kaolin clay, calcined kaolin clay, carbon black, iron oxide black, iron oxide yellow,iron oxide red, iron oxide brown, organic red pigments, including quinacridone red and metallized and non-metallized azo reds (e.g., lithols, lithol rubine, toluidine red, naphthol red), phthalocyanine blue, phthalocyanine green, mono- or di -arylide yellow, benzimidazolone yellow, heterocyclic yellow, quinacridone magenta, quinacridone violet, and the like, and any combination thereof. In some embodiments, the pigment is selected from the group consisting of titanium dioxide, clay, silica, diatomaceous silica, calcium carbonate, talc, zinc oxide, mica, red oxide, hansa yellow, phthalo blue, and yellow ochre.

[0069] In some embodiments, the pigment may be a special effect pigment. Examples of special effect pigments are metal pigments, for example, from aluminum or copper, interference pigments, such as, for example, aluminum coated with titanium dioxide, coated mica, graphite effect pigments and iron oxide laminae. Some special effect pigment may be inhibitor and / or extender pigments. Inhibitors, such as rust inhibitors, are pigments that have little to no corrosive action. For example, metal pigments are commonly used to protect metallic surfaces from corrosion. Nonlimiting exemplary inhibitor pigments include zinc, chromate, phosphate, and borate based pigments. Extender pigments are typically added to paints and coatings to reduce the cost of formulations. They may also be used to modify the viscosity, sedimentation stability, and / or film strength. Commonly, extender pigments appear white and possess a refractive index similar to commonly used binders. Nonlimiting exemplary extender pigments include clay, silica, and mica.

[0070] In some embodiments, the compositions of the present technology may include from about 0 wt% or from about 5 wt% to about 75 wt% pigment based on the total weight of the composition. In some embodiments, the compositions may include 0 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 75 wt% of pigment, or a range between and including any two of the foregoing. In some embodiments, the composition include from 0 wt% to about 50 wt%, or from about 10 wt% to about 30 wt% pigment based on the total weight of the composition.Other ingredients

[0071] The compositions described herein (e.g., the paint or coating compositions), in addition to comprising an additive (e.g., one or more selected from a compound of Formula (I) and additional neutralizing agents), a binder, a pigment, and water, may also include one or more cosolvents and / or other ingredients.

[0072] In some embodiments, a composition as described herein may comprise one or more cosolvents.

[0073] The carrier is the solvent in which composition materials are dissolved, dispersed, and / or suspended. In the compositions of the present technology, the carrier is water, although other water-based solutions such as water-alcohol mixtures and the like may be used. The aqueous carrier generally makes up the balance of the composition, after all the other ingredients have been accounted for. In some embodiments, the composition may include a cosolvent such as an organic solvent. For example, the cosolvent may be an alcohol (e.g., methanol, ethanol, or isopropyl alcohol), glycol ether such as ethylene glycol, diethylene glycol, and / or propylene glycol (e.g., propylene glycol C1-C4 alkyl ether, C1-C4 alkoxyethanol such as butoxyethanol), a heterocycle such as a lactone (e.g., N-methyl-2- pyrrolidone), glycerin, or a combination thereof. Cosolvents are sometimes present in the composition to aid in film formation, to resist freezing, and / or enhance brushing properties, such as by increasing open time. Open time is the time that a coating remains workable after it has been applied to a substrate. Open time allows for rebrushing or "melting in" of the newly applied coating at the lap, without causing brush marks, loss of gloss, or lap lines in the final dried coating. A lap is an area on a substrate where additional coating is applied onto a portion of a previously coated, but still wet, adjacent substrate area. In some embodiments, the compositions may include no more than about 15 wt% cosolvent (e.g., 1- 15 wt%), based on total composition. Alternatively, the compositions may include no more than about 10 wt% cosolvent or no more than about 5 wt% cosolvent (e.g., 1-10 or 1-5 wt%).

[0074] In some embodiments, a composition as described herein may comprise one or more other ingredients. For example, the composition may further include a dispersing agent. The dispersing agent may be present at an effective amount, e.g., 0.01 wt% to 1 wt% of thecomposition. In some embodiments, the amount of dispersing agent in the composition may be 0.01, 0.02, 0.05, 0.075, 0.1, 0.2, 0.3, 0.4 0.5, 0.6, 0.7, 0.8, 0.9, or 1 wt% or a range between and including any two of the foregoing values. Dispersing agents are soluble materials whose physicochemical adsorption to the surface of pigment particles stabilizes the dispersion of the pigment particles against reagglomeration. Illustrative dispersing agents include, but are not limited to, salts of polyacrylic acids or modified polyacrylic acids, and polyphosphate salts such as sodium hexametaphosphate.

[0075] Other ingredients may be included in the compositions including, but not limited to, coalescents, leveling agents and surfactants, thickeners (e.g., cross-linked poly carboxylic acid or polyurethanes), rheology modifiers (e.g., highly disperse silicic acid or polymeric urea compounds), corrosion inhibitors, defoamers, wetting agents, dispersants, biocides, flow control agents based on (meth)acrylic homopolymers or silicon oils, or combinations of two or more thereof. Such ingredients may provide specific properties to the composition and / or the film, such as mildew resistance, defoaming, light stability, and / or good flow and leveling during application. For example, the compositions may include one or more ingredients selected from the group consisting of leveling agents, surfactants, thickeners, rheology modifiers, co-solvents, corrosion inhibitors, defoamers, co-dispersants, additional neutralizer(s), and biocides. Such ingredients may be added in the usual amounts familiar to the person skilled in the art. In some embodiments, the compositions of the present technology may include from about 0 wt% to about 75 wt% one or more ingredients selected from the group consisting of leveling agents, surfactants, thickeners, rheology modifiers, cosolvents, corrosion inhibitors, defoamers, co-dispersants, additional neutralize^ s), and biocides, based on the total weight of the composition. In some embodiments, the compositions may include 0 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 75 wt% of one or more ingredients selected from the group consisting of leveling agents, surfactants, thickeners, rheology modifiers, co-solvents, corrosion inhibitors, defoamers, co-dispersants, additional neutralize^ s), and biocides, or a range between and including any two of the foregoing.

[0076] Leveling agents may be added to change the surface tension and improve wetting. Leveling agents are a subset of surfactants used to ensure that a composition flows out over and completely wets the surface being coated. Reduced contact angles between the composition and the surface lead to better flow leveling, and better surface wetting allows for better adhesion of the composition and the physically coalesced and / or chemically cured film. Surfactants are also important as grinding aids for pigment grinding operations. In some embodiments, the compositions of the present technology may include from about 0 wt% to about 75 wt% surfactants (e.g., leveling agents) based on the total weight of the composition. In some embodiments, the compositions may include 0 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 75 wt% of surfactants (e.g., leveling agents), or a range between and including any two of the foregoing.

[0077] Thickeners may be used to obtain the desired degree of viscosity needed for the proper formulation and application of the composition. One general type of thickener is referred to in the art by the term "associative." Associative thickeners are so called because the mechanism by which they thicken is believed to involve hydrophobic associations between the hydrophobic moieties in the thickener molecules and / or between the hydrophobic moieties in the thickener molecules and other hydrophobic surfaces. One type of commonly used associative thickener has a polymeric backbone constructed from one or more blocks of polymerized oxyalkylene units, typically polyethylene oxide or polypropylene oxide, with hydrophobic groups attached to or within the backbone. Another type of commonly used associative thickener utilizes a cellulosic backbone with hydrophobic groups attached to the backbone. Both of these types of associative thickeners can be characterized as polyether thickeners as they both have backbones comprising ether linkages. Known polyether associative thickeners are non-ionic thickeners, and their thickening efficiencies in aqueous systems are substantially independent of pH. Other thickeners may also be included in the compositions such as those described in U.S. Patent No. 7,741,402, which is herein incorporated by reference. In some embodiments, the compositions of the present technology may include from about 0 wt% to about 75 wt% thickeners based on the total weight of the composition. In some embodiments, the compositions may include 0 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%,about 50 wt%, about 60 wt%, about 75 wt% of thickeners, or a range between and including any two of the foregoing.

[0078] Rheology modifiers may be added to thicken the compositions and to increase its yield stress, thus allowing for the formation of a stable suspension of pigments in resin upon mixing. Rheology modifiers are also added to optimize the application properties of the composition. In some embodiments, the compositions of the present technology may include from about 0 wt% to about 75 wt% rheology modifiers based on the total weight of the composition. In some embodiments, the compositions may include 0 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 75 wt% of rheology modifiers, or a range between and including any two of the foregoing. Pigment dispersants are added to create a stable dispersion of the pigment. Pigment dispersants function by directly interacting with pigment particles both mechanically and electrostatically. Rheology modifiers function by increasing the yield stress of the water-resin system.

[0079] Corrosion inhibitors and flash rust inhibitors can suppress the migration of colored corrosion products from the surface of coated metal objects (e.g., exposed nail heads in dry wall) to the surface of the coating. Also, rust inhibitors may be added to prevent corrosion of iron alloy cans during coating storage. In some embodiments, the compositions of the present technology may include from about 0 wt% to about 75 wt% corrosion inhibitors or flash rust inhibitors based on the total weight of the composition. In some embodiments, the compositions may include 0 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 75 wt% of corrosion inhibitors or flash rust inhibitors, or a range between and including any two of the foregoing.

[0080] Biocides and mildewcides may be added to control microbial growth in the compositions and / or in the film. Microbes can colonize leading to filamentous growths, bad odors and the selective consumption of functional coating ingredients. Some biocides can be added solely to control microbes during storage of the composition (so called in-can biocides) while other biocides are added to impart biostability to the coalesced / cured film (so called dryfilm biocides). Some biocides can prevent both in-can and dry film biological growth. Typical biocides include isothiazolinones, such as 5-chloro-2-methyl-4-isothizolin-3-one; benzoisothiazolinones; triazines, such as hexahydro-1, 3, 5-tris-2-hydroxyethyl-s-triazine; 1- (3-chloroallyl)-3,5,7-triaza-l-azoniaadamantane chloride (DOWICIL® 75); zinc pyrithione; gluteraldehyde; bronopol; and phenolics. In some embodiments, the compositions of the present technology may include from about 0 wt% to about 75 wt% biocides or mildewcides based on the total weight of the composition. In some embodiments, the compositions may include 0 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 75 wt% of biocides or mildewcides, or a range between and including any two of the foregoing.

[0081] Defoamers are special types of surfactants that have the effect of decreasing the foaminess of an agitated coating compositions, when it is manufactured, when it is shaken or stirred, and when it is applied to a surface. Defoamers are commercially available under a number of tradenames such as, for example, FOAMASTER®, ADVANTAGE® 1512, and BYK® 1650. In some embodiments, the compositions of the present technology may include from about 0 wt% to about 75 wt% defoamers based on the total weight of the composition. In some embodiments, the compositions may include 0 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 75 wt% of defoamers, or a range between and including any two of the foregoing.

[0082] In some embodiments, the present compositions may include fillers. Nonlimiting examples of fillers are silicon dioxide, barium sulfate, talcum, calcium carbonate, aluminum silicate and magnesium silicate. In some embodiments, the compositions of the present technology may include from about 0 wt% to about 75 wt% fillers based on the total weight of the composition. In some embodiments, the compositions may include 0 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 75 wt% of fillers, or a range between and including any two of the foregoing.

[0083] In some embodiments, the composition may be substantially free of low molecular weight surfactants. In some embodiments, the composition does not contain low molecular weight surfactants.Methods and use of the compositions

[0084] In accordance with any of the foregoing embodiments, also provided herein is a method for reducing the volatile organic compound content of a composition comprising an aqueous dispersion of a polymeric binder resin and a pigment, the method comprising using an effective amount of a neutralizing agent in the composition wherein the neutralizing agent comprises the additive described herein (e.g., a compound of Formula (I)). In some embodiments, the neutralizing agent may comprise or may be Compound 1. In some embodiments, the neutralizing agent may comprise or may be Compound 13. In some embodiments, the neutralizing agent may comprise or may be a combination of Compound 1 and Compound 13. In some embodiments, the composition may be substantially free of volatile organic compound content. In some embodiments, the composition is a coating composition or a paint.

[0085] In a further aspect, provided herein is a method for reducing toxicity of a coating composition comprising an aqueous dispersion of a polymeric binder resin and a pigment, the method comprising using as a neutralizing agent in the paint or coating an effective amount of the additive described herein (e.g., a compound of Formula (I)). In some embodiments, the neutralizing agent may comprise or may be Compound 1. In some embodiments, the neutralizing agent may comprise or may be Compound 13. In some embodiments, the neutralizing agent may comprise or may be a combination of Compound 1 and Compound 13. In some embodiments, the composition described herein does not have one or more of respiratory sensitization, carcinogenicity, mutagenicity, reproductive toxicity, or ecotoxicity.

[0086] In another aspect, provided herein is a method comprising adding to a composition comprising an aqueous dispersion comprising a pigment and / or polymer binder resin an effective amount of the additive described herein (e.g., a compound of Formula (I)) to raise the pH of the composition, stabilize the composition, and / or at least partially neutralize any acidic compounds in the composition. In some embodiments, the pH of thecomposition may be raised to about 7 to about 13 or about 7 to about 10. In some embodiments, the composition is stable for at least about 1 month, at least about 2 months, at least about 3 months, at least about 6 months, at least about 12 months, or at least about 24 months. In some embodiments, the additive neutralizes at least about 20% of the acid functional groups on the polymeric binder (e.g., at least about 30%, at least about 40%, or at least about 50%). In some embodiments, the additive neutralizes about 20% to about 100% of the acid functional groups on the polymeric binder (e.g., about 30% to about 90% or about 40% to about 80%.

[0087] Any embodiments of the compositions described herein may be film forming compositions. The films derived from the compositions may have any thickness; for example, such films may have a thickness in the range of from 0.1 pm to 10 mm; or in the alternative, from 1 pm to 1000 pm; or in the alternative, from 5 pm to 500 pm; or in the alternative, from 10 to 100 pm; or in the alternative, from 10 pm to 80 pm; or in the alternative, from 10 to 50 pm.

[0088] In some embodiments, the composition described herein is a coating. In some embodiments, the composition described herein is a latex paint. Accordingly, the present technology provides a coating comprising the dried composition (e.g., a dried layer or coating on a substrate) according to any one of the embodiments described herein.

[0089] The paints and / or coatings provided herein can be used for example, in different coating applications such as residential and / or industrial coating applications, architectural coating applications, automotive coating applications, outdoor furniture coating applications, exteriors and interiors of houses, and other buildings.

[0090] The compositions as described herein may be applied by means of conventional application methods, for example, by rolling, brushing, dipping, or spraying onto any desired uncoated or pre-coated substrate. The surface of such structures to be coated with the compositions may comprise concrete, wood, metal, plastic, glass, drywall, or the like. Once applied, drying / coalescing may then proceed at ambient temperature or elevated temperatures (e.g., about 25 °C to about 300 °C including about 50 °C to about 180 °C) depending on the composition.

[0091] Accordingly, the present technology provides a coating that includes the physically coalesced composition. In some embodiments, the composition may be physically coalesced at temperatures ranging from about 0 °C to about 300 °C. In some embodiments, the composition may be physically coalesced at temperatures of at least about 5 °C. In some embodiments, the temperatures may be at least about 10 °C. In some embodiments, the temperatures may be at least about 15 °C. For example, the composition may be physically coalesced at about room temperature. In some embodiments, the composition may be physically coalesced after about 60 minutes, after about 5 hours, after about 10 hours, after about 15 hours, or after about 1 day. For example, the composition may be physically coalesced after about 60 minutes to about 1 week, about 5 hours to about 12 days, about 10 hours to about 10 days, or about 1 day to about 7 days.Methods of manufacturing the compositions

[0092] The compositions described herein may be manufactured by conventional paint and coating manufacturing techniques, which are well known to those skilled in the art. Typically, the compositions are manufactured by a two-step process. First, a dispersion phase, commonly referred to as the grind phase, is prepared by mixing the dry pigments with other grind phase components, including most other solid powder formulation materials, under high shear agitation to provide a high viscosity and high solids mixture. This part of the process is designed to effectively wet and dis-agglomerate the dry pigments to a finely dispersed state.

[0093] The second step of the paint / coating manufacturing process is commonly referred to as the letdown or thindown phase, because the viscous grind is diluted with the remaining formulation components, which are generally less viscous than the grind mix. Typically, the binder, any predispersed pigments, and any other paint / coating ingredients that only require mixing and perhaps moderate shear, are incorporated during the letdown phase. The letdown phase may be done either by sequentially adding the letdown components into a vessel containing the grind mix, or by adding the grind mix into a vessel containing a premix of the binder and other letdown components, followed by sequential addition of the final letdowncomponents. In either case, constant agitation is needed, although application of high shear is not required. For a clear coating without pigments, the grinding step may be excluded.

[0094] The additive (e.g., a compound of Formula (I) may be added to the composition at one or more of three different places in the manufacturing process: to the pigment dispersion (grinding), to the binder dispersion (letdown), and / or in a final addition to the composition.

[0095] In another aspect the present technology contemplates a process for preparing a coating layer, which includes:1) applying a coating layer from a composition provided herein; and2) drying / coalescing the coating layer. Optionally, the applied coating layer may be flashed off to remove water and organic solvent, if present.

[0096] Unless otherwise indicated, numeric ranges, for instance as in "from 2 to 10," are inclusive of the numbers defining the range (e.g., 2 and 10).

[0097] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.EXAMPLES

[0098] The examples herein are provided to illustrate advantages of the present technology and to further assist a person of ordinary skill in the art with preparing or using the compositions of the present technology. The examples herein are also presented in order to more fully illustrate the preferred aspects of the present technology. The examples should in no way be construed as limiting the scope of the present technology, as defined by the appended claims. The examples can include or incorporate any of the variations, aspects or aspects of the present technology described above. The variations, aspects or aspects described above may also further each include or incorporate the variations of any or all other variations, aspects or aspects of the present technology.

[0099] General Information.

[0100] The IUPAC names and abbreviations of the compounds tested herein are provided in below table.Example 1. Synthesis of the compounds

[0101] The compounds described herein (e.g., a compound of Formula (I)) can be prepared according to methods known in the art (e.g., through hydrogenation or alkoxylation reaction), including the exemplary syntheses of Compound 1 and Compound 13 provided herein.

[0102] Compound 1 (2,2'-((2-amino-2-methylpropyl)azanediyl)bis(ethan-l-ol)) may be prepared, e.g., using the procedure set forth in US 2,393,825 to Senkus. Briefly, the corresponding nitroamine (e.g., 2,2'-((2-methyl-2-nitropropyl)azanediyl)bis(ethan-l-ol)) is subjected to catalytic liquid phase high pressure hydrogenation to give Compound 1, also known as 3-(2-aminoisobutyl) 3 -aza- 1,5 -pentane diol. The boiling point of the product is 178 °C @ 9.4 mmHg. *H NMR CDC135 (ppm): 1.10 (s, 6H, CH3), 2.44 (s, 2H, CH2), 2.68 (t, 4H, CH2), 3.53 (b, 4H, OH / NH), 3.56 (t, 4H, CH2).

[0103] Compound 13 (2,2'-(ethane-l,2-diylbis(methylazanediyl))bis(ethan-l-ol)) may be prepared, e.g., using the procedure set forth in GB 2,279, 949A to Hora et al. Briefly, the corresponding oxazolidine (e.g., 3,3’-dimethyl-2,2’-bioxazolidine) is subjected to catalytic liquid phase high pressure hydrogenation. The product (Compound 13) is a colorless liquid. 'H NMR CDCh 5 (ppm): 2.33 (s, 6H, CH3), 2.55 (t, 4H, CH2), 2.57 (t, 4H, CH2), 3.60 (dt, 4H, CH2), 4.58 (b, 2H, OH).Example 2a. Evaluation of the VOC status of the additives

[0104] The VOC status of the compounds were evaluated using gas chromatography. The corresponding results were then compared to GB 18582-2020 Standard (GB 18582-2020 Limit of harmful substances of architectural wall coatings), in which the limit of VOC content for a paint product is 80 g / L. It was found that the corresponding results for Compound 1, AEPD, and NBDEA were 0.9732 g / L, 436 g / L, and 2 g / L, respectively.Example 2b. Colorimetric evolution of the additives

[0105] We sought to verify the colorimetric evolution of the additives over time under 50°C: a first measurement was carried out at room temperature, and the samples were then placed in an oven at 50°C. The L, a, b values of these samples were measured weekly, results are shown in FIG. 16.Example 3. Neutralizing efficiency

[0106] The neutralization efficiency of different additives (AMP, AEPD, NaOH, NBDEA, Compound 1, and Compound 13, respectively) was evaluated by titration with HC1. As shown in FIG. 1, Compound l is a very strong neutralizer, which is due to the presence of two amines groups including one tertiary. According to the titration curve of FIG. 1, the pKa of Compound 1 can be estimate as about 10.6. Additionally, Compound 1 can neutralize the pH with the lowest loading compared to NBDEA and AEPD. Moreover, Compound 1 can buffer the pH because of being a weak base, which is not achievable when using a strong inorganic based such as NaOH.Example 4. TiOi wetting efficiency

[0107] The ability of wetting and dispersing pigments (e.g., TiCh), is a very important criteria for quality. Dispersant demand curves of a conventional polyacrylic dispersant (Orotan® 731 from Dow) in presence of the different additives was carried out (FIGS. 4a- 4b) The Krebs viscosity of a TiCh slurry was measured while the dispersing agent (Orotan® 731 from Dow) was added drop by drop. The wetting and dispersing ability of the corresponding additives was also evaluated without the support of any other dispersing agents (e.g., without Orotan® 731, FIGS. 2-3). The additives being tested in the study are summarized in Table A below.

[0108] As shown in FIGS. 2-4, Compound 1 provides an outstanding performance compared to the other additives.Table A.Example 5. Water based paint performance

[0109] Aiming to address the complexity of an evaluation of a paint formulation, a statistical approach based on the Design of Experiment (DoE) method was implemented. A DoE with 5 variables for each neutralizer / additive was set up, and the results were compared statistically. Table 1 below illustrates the DoE generated with the neutralizer / additive tested, containing 16 runs of the DoE and a control. The 5 parameters of the DoE were:• AA concentration: the original dosage point was selected (0.12% in molar equivalent of the neutralizer / additive tested), and half of this regular dosage was also tested in order to challenge the efficiency of the AA. Depending on the additive, some adjustments were implemented (further explained in the following paragraph) and shown in Table 2.• Dispersing agent concentration: the low level corresponded to a concentration slightly above the minimum determined by a dispersant demand curve, and the high level of 0,1% corresponded to the typical recommendation of the supplier.• TiCh concentration: two levels for the determination of the potential TiCh reduction based on the better dispersing efficiency.• Binder concentration: two levels for the determination of the potential binder reduction based on the better latex stabilization.Dispersing time: the low level was 7 minutes which was the faster dispersion time according to our experience with our disperser, and the high level of 20 minutes was to ensure a full dispersion of pigments.Table 1. Design of Experiment of the decorative paint with neutralizer / additive tested.Table 2. Composition of the satin decorative paint.Table 3. Molar and weight dosages of all additives for each level of the Design ofExperiments (DoE).Preparation of the paint

[0110] All the formulations were prepared with a Dispermat AE. A dispersing disk was used. For a 1 L bowl: 65 mm f (blade size). The ingredients were incorporated step by step, the dispersion time and speed of the motor were as indicated in Table 2. Properties of eachpaint were measured during 3 months, including the pH, viscosity (ICI, Brookfield with two speeds), gloss (20°, 60°, 85° angles), spectrocolorimetric test (L*a*b*, and contrast ratio), the dry film hardness, and the wet scrub resistance.Analyses of the DoE

[0111] Analysis of the pH. The pH was measured with a pH-meter Seven2Go S2, with electrode from Inlab Viscous Pro.

[0112] After the aging test of 3 months at room temperature (FIG. 5A-5D), AMP-95 and Compound 1 were the products leading to better pH stability during storage. AEPD was showing some weaknesses, despite a pKaof 8.7, which was equal to the pH of the paint. Compound 1 was slightly better compared to NBDEA at low concentration (FIGS. 6A-6B).

[0113] Analysis of the Gloss. Gloss measurements were made using a BYK Gardner Tri-Gloss Meter calibrated once per day. Unless otherwise noted, drawdowns were performed using a 150 micrometers wet film thickness applicator using an automatic applicator device as Elcometer 4340. A drying step was systematically implemented during 24 hours at 23°RH. The 20°, 60° and 85°gloss values were reported.

[0114] Initial distribution of gloss measurements at all angles are shown in FIG. 7. The mean of AMP, Compound 1, and NBDEA were the lowest, and AEPD was clearly not as good as other additives, even worse than NaOH. According to the variability of the gloss, given by the wideness of the box plot (or the variance in FIG. 9), AMP and Compound 1 were the best candidates, NBDEA can be classified right after (if two outliers in the statistical analyze highlighted by the two black dots at the top of the box plot were removed).According to the results including the two levels of additive concentration (FIG. 8), it is shown that the broadness of the box plot can be due to a higher efficiency of the product at low concentration. Both AMP and Compound 1 were developing a low gloss already with the lower concentration, while other additives, including NBDEA, required the higher level of concentration. Even at the high concentration, AEPD didn’t reach the gloss value of other additives. This is a confirmation of the higher required dosage of AEPD compared to incumbent products.

[0115] Analysis of the L*a*b*. Contrast ratio was measured by first drawing down coatings onto Leneta opacity charts using a 150 micrometer wet film thickness applicator. Coatings were dried overnight before measuring L-reflectance using Spectrophotometre CM- 5 Konica Minolta calibrated once per day the values are averages of three measurements across the drawdown surface over the white and black areas. Contrast ratio was calculated by dividing the L-reflectance measured over black by the L-reflectance measured over white, multiplied by 100.

[0116] It was found that the L*a*b* initial values could lead to several interesting points. First, the overall comparison in FIG. 10 shows the difference between additives tested. Compound 1 and NBDEA were developing the highest brightness, AEPD was the lowest in this comparison. At the same time, Compound 1 and NBDEA had a higher initial -a* value (more greenish paint), and a slightly lower b* value (less yellowish). The impact of alkanolamine on b* is known, but the results on a* is very surprising. The analysis of the same results, but spitted by the two concentrations of the additives is shown in FIG. 11.

[0117] Analysis of the Contrast Ratio. It was found that the results in contrast ratio could vary significantly with the nature of the additive (FIG. 13). First of all, NBDEA and Compound 1 were showing the best initial results (highest CR means). In addition, NaOH developed a very high variability of the data, highlighting the link between TiCh stabilization provided by alkanolamines and CR.

[0118] Further, the stability of contrast ratio after natural aging of the paint (3 months at room temperature) stressed a slightly better stability of Compound 1 in comparison of NBDEA (FIG. 14).

[0119] Analysis of the Hardness. The following procedure was based on ASTM D4366 and ISO 1522. Drawdowns were performed using a 150 micrometers wet film thickness applicator onto glass panels. Measurements were made after an overnight dry (Day 1) and then weekly thereafter for four weeks. Hardness values were reported as elapsed seconds for the amplitude of swing to decrease from 6° to 3°.

[0120] It was found that Compound 1, like AMP, could lead to the highest hardness of the film (FIG. 15). In view of the different pKa between these products, it appears that higher pKa can support slightly higher hardness.

[0121] Analysis of the Toxicity. Toxicity modeling data was generated using commercially available modeling software (QSAR Toolbox and EPI Suite™). The results indicated no alerts for skin and respiratory sensitization, carcinogenicity, mutagenicity, reproductive toxicity, or ecotoxicity.Discussion

[0122] In sum, Compound 1 is an additive with several advantages including a very strong neutralizing efficiency based on a high pKa, a positive impact on gloss and hiding power, and the absence of detrimental effect on other parameters of the paint. Table 4 below summarizes the comparative results obtained from the DoE methodology.Atty. Dkt. No.: 109691-0777Table 4. Summary of the comparative results based on the DoE methodology.4923-1171-3050 v.4EQUIVALENTS

[0123] While certain embodiments have been illustrated and described, a person with ordinary skill in the art, after reading the foregoing specification, can effect changes, substitutions of equivalents and other types of alterations to the compositions of the present technology as set forth herein. Each aspect and embodiment described above can also have included or incorporated therewith such variations or aspects as disclosed in regard to any or all of the other aspects and embodiments.

[0124] The present technology is also not to be limited in terms of the particular aspects described herein, which are intended as single illustrations of individual aspects of the present technology. Many modifications and variations of this present technology can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods within the scope of the present technology, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. It is to be understood that this present technology is not limited to particular methods, reagents, compounds, or compositions, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only, and is not intended to be limiting. Thus, it is intended that the specification be considered as exemplary only with the breadth, scope and spirit of the present technology indicated only by the appended claims, definitions therein and any equivalents thereof.

[0125] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentiallyof ’ will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of’ excludes any element not specified.

[0126] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the technology. This includes the generic description of the technology with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.

[0127] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0128] All publications, patent applications, issued patents, and other documents (for examplejournals, articles and / or textbooks) referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0129] The present technology may include, but is not limited to, the features and combinations of features recited in the following lettered paragraphs, it being understood thatthe following paragraphs should not be interpreted as limiting the scope of the claims as appended hereto or mandating that all such features must necessarily be included in such claims:A. A composition comprising an aqueous dispersion of a polymeric binder resin and an additive, wherein the additive comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.B. The composition of Paragraph A, wherein the compound of Formula (I) has a structure ofFormula (II)C. The composition of Paragraph A or Paragraph B, wherein R1is CH3 or CH2CH2OH.D. The composition of any one of the preceding Paragraphs, wherein R4and R4are both H or both CH2CH2OH.E. The composition of any one of the preceding Paragraphs, wherein R2, R2, R3, and R3are each independently selected from H, CH3, CH2CH3, or CH2OH.F. The composition of any one of the preceding Paragraphs, wherein the additive is selected from the group consisting of:or a combination of any two or more thereof.G. The composition of any one of the preceding Paragraphs, wherein the additive is:H. The composition of any one of Paragraphs A-F, wherein the additive is:I. The composition of any one of the preceding Paragraphs, wherein the composition comprises about 0.01 wt% to about 10 wt% of the additive.J. The composition of any one of the preceding Paragraphs, wherein the composition comprises about 0.05 wt% to about 2 wt% of the additive.K. The composition of any one of the preceding Paragraphs, wherein the composition comprises about 0.05 wt% to about 0.5 wt% of the additive.L. The composition of any one of the preceding Paragraphs, further comprising a low or zero volatile organic compound neutralizing agent other than the compounds of Formula (I).M. The composition of any one of the preceding Paragraphs, wherein the composition comprises about 10 wt% to about 80 wt% polymeric binder resin.N. The composition of any one of the preceding Paragraphs, wherein the composition comprises about 15 wt% to about 65 wt% polymeric binder resin.O. The composition of any one of the preceding Paragraphs, wherein the polymeric binder resin is selected from the group consisting of a polyacrylate, polyvinyl versatate, polyethylene-vinyl acetate, polyester, or a combination of two or more thereof.P. The composition of any one of the preceding Paragraphs, further comprising about 10 wt% to about 75 wt% pigment.Q. The composition of any one of the preceding Paragraphs, wherein the composition comprises about 10 wt% to about 30 wt% pigment.R. The composition of Paragraph P or Paragraph Q, wherein the pigment comprises titanium dioxide and a colorant.S. The composition of any one of the preceding Paragraphs, further comprising a dispersing agent.T. The composition of any one of the preceding Paragraphs, wherein the composition comprises 0.01 wt% to 1 wt% dispersing agent.U. The composition of any one of the preceding Paragraphs, further comprising one or more of a co-solvent, coalescent, leveling agent, thickener, rheology modifier, corrosion inhibitor, defoamer, wetting agent, dispersant, biocide, flow control agent based on (meth)acrylic homopolymers or silicon oils, or a combinations of any two or more thereof.V. The composition of any one of the preceding Paragraphs, wherein the composition is a coating.W. The composition of Paragraph V, wherein the coating is a latex paint.X. A coating comprising the dried composition of any one of the preceding Paragraphs.Y. A method for reducing the volatile organic compound content of a composition comprising an aqueous dispersion of a polymeric binder resin and a pigment, the method comprising using an effective amount of a neutralizing agent in the composition wherein the neutralizing agent comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided thatthe compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.Z. The method of Paragraph Y, wherein the composition is substantially free of volatile organic compound content.AA. The method of Paragraph Y or Paragraph Z, wherein the composition is a coating composition or a paint.AB. A method for reducing toxicity of a coating composition comprising an aqueous dispersion of a polymeric binder resin and a pigment, the method comprising using as a neutralizing agent in the paint or coating an effective amount of a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.AC. A method comprising adding to a composition comprising an aqueous dispersion comprising a pigment and / or polymer binder resin an effective amount of an additive to raise the pH of the composition, stabilize the composition, and / or at least partially neutralize any acidic compounds in the composition, wherein the additive comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.

[0130] Other embodiments are set forth in the following claims, along with the full scope of equivalents to which such claims are entitled.

Claims

WHAT IS CLAIMED IS:

1. A composition comprising an aqueous dispersion of a polymeric binder resin and an additive, wherein the additive comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.

2. The composition of claim 1, wherein the compound of Formula (I) has a structure ofFormula (II)3. The composition of claim 1 or claim 2, wherein R1is CH3 or CH2CH2OH.

4. The composition of claim 1 or claim 2, wherein R4and R4are both H or bothCH2CH2OH.

5. The composition of claim 1 or claim 2, wherein R2, R2, R3, and R3are each independently selected from H, CH3, CH2CH3, or CH2OH.

6. The composition of claim 1 or claim 2, wherein the additive is selected from the group consisting of:, and, or a combination of any two or more thereof.

7. The composition of claim 1 or claim 2, wherein the additive is:

8. The composition of claim 1 or claim 2, wherein the additive is:

9. The composition of claim 1 or claim 2, wherein the composition comprises about 0.01 wt% to about 10 wt% of the additive.

10. The composition of claim 1 or claim 2, wherein the composition comprises about 0.05 wt% to about 2 wt% of the additive.

11. The composition of claim 1 or claim 2, wherein the composition comprises about 0.05 wt% to about 0.5 wt% of the additive.

12. The composition of claim 1 or claim 2, further comprising a low or zero volatile organic compound neutralizing agent other than the compounds of Formula (I).

13. The composition of claim 1 or claim 2, wherein the composition comprises about 10 wt% to about 80 wt% polymeric binder resin.

14. The composition of claim 1 or claim 2, wherein the composition comprises about 15 wt% to about 65 wt% polymeric binder resin.

15. The composition of claim 1 or claim 2, wherein the polymeric binder resin is selected from the group consisting of a polyacrylate, polyvinyl versatate, polyethylene-vinyl acetate, polyester, or a combination of two or more thereof.

16. The composition of claim 1, further comprising about 10 wt% to about 75 wt% pigment.

17. The composition of claim 1, wherein the composition comprises about 10 wt% to about30 wt% pigment.

18. The composition of claim 16 or claim 17, wherein the pigment comprises titanium dioxide and a colorant.

19. The composition of claim 1 or claim 2, further comprising a dispersing agent.

20. The composition of claim 1 or claim 2, wherein the composition comprises 0.01 wt% to1 wt% dispersing agent.

21. The composition of claim 1 or claim 2, further comprising one or more of a co-solvent, coalescent, leveling agent, thickener, rheology modifier, corrosion inhibitor, defoamer, wetting agent, dispersant, biocide, flow control agent based on (meth)acrylic homopolymers or silicon oils, or a combinations of any two or more thereof.

22. The composition of claim 1, wherein the composition is a coating.

23. The composition of claim 22, wherein the coating is a latex paint.

24. A coating comprising the dried composition of claim 1 or claim 2.

25. A method for reducing the volatile organic compound content of a composition comprising an aqueous dispersion of a polymeric binder resin and a pigment, the method comprising using an effective amount of a neutralizing agent in the composition wherein the neutralizing agent comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.

26. The method of claim 25, wherein the composition is substantially free of volatile organic compound content.

27. The method of claim 25 or claim 26, wherein the composition is a coating composition or a paint.

28. A method for reducing toxicity of a coating composition comprising an aqueous dispersion of a polymeric binder resin and a pigment, the method comprising using as a neutralizing agent in the paint or coating an effective amount of a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.

29. A method comprising adding to a composition comprising an aqueous dispersion comprising a pigment and / or polymer binder resin an effective amount of an additive to raise the pH of the composition, stabilize the composition, and / or at least partially neutralize any acidic compounds in the composition, wherein the additive comprises a compound of Formula (I),whereinR2, R2, R3, and R3are each independently H or a C1-2 alkyl optionally substituted with OH;R1and R1are each independently Ci-4 alkyl optionally substituted with OH;R4, R4are both H or both Ci-4 alkyl optionally substituted with OH; provided that the compound of Formula (I) has 1 or 2 hydroxy groups and 6, 7, 8, 9, or 10 carbon atoms.

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